Bobebt halleb



Patented Sept. 6, 1932 UNITED- S $Y NT. OFFICE) Ro'BEn-THA LER, or RIEHEN, NEAR BAsEL, SWITZERLAND, ASSIGNOR To SOCIETY OF CHEMICAL INDUSTRY IN nAsLE; or. BASEL, SWITZERLAND PROCESS FOR PRODUCING FAST TINTS ON FIBER No'D'raWing. Application filed August 29, 1929, Serial 110.389,.324, and in Switzerland September 7, 192s.

, The present invention relates to a new process for producing fast tints on the fiber. It comprises the new process, the new dyestuffs and the material which has been dyed with the new dyestuffs.

The production of fast tints on the fiber by uniting usual coupling components with diazotizing components is well-known.

The present invention isbased on the surprising discovery that very valuable dyeings can be produced on materials by treating the latter, which have been impregnated with leuco-compounds, with diazo-compounds. By

the conception leuco-compounds there are to be understood the leuco-compounds from dyestuffs, as well as the leuco-compounds fromother products, and the ester salts which the said leuco-compounds can form with monoor bivalent acids. There are thus obtained dyeingsthat are characterized by their intensity and. their fastness properties.

The process maybe conducted in'a very simple manner. For example, the goods to be dyed,such as fibrous material, are satu rated in the vat, thoroughly pressed, rinsed in a bath containing a small quantity of sodium hydrosulfite and an alkali, again pressed and then introduced into a solution of a dia-zo-compound, whereupon coupling immediately occurs with formation of the dyestuff on the material. Both the opera tion of saturating the material with the leucocompound and the coupling operation may be conducted in presence of assistants, such as s a protective colloid, a wetting agent, a dispersing agent or the like. Inthis manner there is produced a dyeing which,-according to the nature of the leuco-compound and diazo-compound used, may differ completely from the normal dyeing produced by the vatdyestufl. The dyeings obtainable in accordance with the invention are in part distinguished by remarkable properties of fastness, which often surpass those of the dyeing produced by the vat-dyestufl' used.

The invention is applicable for dyeing all materials which are capable of being dyed by means of vatdyestufi'sg among others, various'textilematerials, such as cotton,

wool, loaded or unloaded silk and artificial fibrous material of all kinds.

The following examples illustrate the invention I l Example 1 The parent vat is ing manner:

1 kilo of Ciba Blue 2B (of; Schultz, 1914, No. 881) in powder form or the corresponding quantity of the dyestufi" in paste form is made into a paste with 100 grams of Solapol oil F (strongly sulfonated castor oil), or a similar assistant, and 150 litres of hot water. There are then added 2.5 litres of a caustic soda solution of 36 Be. and 2 kilos of hydrosulfite concentrated powder are gradually strewn into the liquid whilst stir ring.

At C. the dyestuff is reduced in 10 to 15 minutes, whereupon the parent vat thus formed 18 added to the dyeing vat to which some hydrosulfite and caustic soda have pre-' viously been added. The goods are introduced and allowed to remain in the vat for hour at 60 C. in the manner usual time inwater, pressed and introduced into. a diazo-solution prepared in the following manner 1 10 parts of the dyestuff prepared by coupling diazo-benzene and a-naphthylamine and 15 parts of hydrochloric acid of 20 B.

are stirred together with 500 parts of 051d water. lVithin 5 minutes there are added 3.5 parts of sodium nitrite dissolved in. 50 parts of water, and stirring is continuedvfor hour. The whole is then filtered, made up to 1000 parts by adding cold water, adding before couplingiZO parts of sodiumacetate. I I

The material is dyed an intense brown fast to chlorine.

A similar shade is obtained inthe follow-.

ing manner 9 parts of the sodium salt sulfuricprepared in the follow- Cibanone dyestufis and rinsed in the acid ester of the leuco-tetrabromindigo are dissolved in parts of warm water. There are then added lOO parts of cold water, 200 parts of anhydrous sodium sulfate, 200 parts Q of cold water, and 5 parts of Turlrey red The goods are impre ated with a 1 the pi oouct. of the sulfurization of anthracene (cf.'

U. S. Patent No. 922,282) in a strongly allialine vat in the manner usual in dyeing with manner indicated in Example l.

Coupling is conducted in the manner indicated in Example 1, the goods being developed in a diaZo-solution prepared in the following manner 7 8 parts of -124:-diaminoQ-methyl-5-methoxy-lzl'azobenzene are dissolved in 500 1 parts of cold water and 36 parts of hydrochloric acid of 20 1%. Within 5 minutes there is added a solution of parts of sodium nitrite in 50 parts of water, and he whole is allowed to stand for 15 miuutesafter which time diazotization is complete. Be-

fore use, the solution is made up to 1000 parts by the addition of cold water, and neutralized by the addition of 89 parts of a r 1 t ll 1' t- 90 so u 1011 O1 sot rum acc are or per ccn.

to 1 hour, 20 grams ofGlaubers salt per litre of the dyebath being added if necessary in order to improve the absorption of the leuco-compound by the goods.

The goods impregnated with the leucocompound as above described are rinsed in an alkaline hydrosulfite bath in the manner indicated in Example 1, rinsed in fresh water and introduced into a diazo-solution prepared in the following manner '8 grams of benzene-azo-a-napththylamine and 15 cc. of hydrochloric acid of 20 B. are stirred with 500 cc. of cold water. Within 5 minutes there is added a solution 01 93.5 grams of sodium nitrite in 50 cc. of water and stirring is continued for hour. Be-

fore use, the solution is filtered, made up with.

cold water to 1 litre and neutralized with 50 cc.- of a solution of sodium acetate of 20 per cent. strength, so that it no longer colours Congo paper blue. In this manner there is produced a very intense olive dyeing.

Instead of aininoazowompoundsthere may obviously be used diazo-components of simpler constitution derlved from amlnes of the benzene or napththlene series, such as diazobenzene, dIQZOrtOl- BIIQ, diazo-napththalene and nuclear substitution products of these compounds. Generally, however, deeper p m snades are produced by using an amlnoazocompound as diazo-component.

.The following table shows the tints which can beobtained by some of the numerous combinations in accordance with the invenstrength. tion, the name Schultz referring to G. Beautlful full brown tints are produced. Schultz, Farbstofi'tabellen, edition 1914.

Leuco-compound Blaze-compound '1 int 1. Ciba violet B (Schultz No. 901) 4-ch1oro-2-amino-diphenylether Red-brown. 2. Ciha violet B idem Aminoazotoluene .Red-brown. 3. Ciba yellow G (Schultz No. 890). Ortho-phenetidine Dull yellow. 4. Ciba yellow G .idcm Benzene-azo-a-naphthylamine. Yellow brown. 5. Cibanone blue RS (Colour Index N o. 1106) Benzene-azo-a-naphthylamine Dark red-brown. 6. Ciba heliotrope B (Schultz No. 897) 4-chloroA-amino-2-methyl-5-methoxy-1:1 Bordeaux. 7. Ciba violet 3B (Schultz No. 900)." Benzene-azo-a-naphthylamine Deep'brown. 8. Ciba bordeaux B (Schultz No. 919) 4: 4'41larnlno-2-methyl-5-ncthcity 1:1-azobenzene Red-brown. 9. Ciba rose B (Colour Index No. 1207). Benzene-azo-a-naphthylamine Brown. 1

10. Ciba Scarlet G (Schultz N o. 907) 4: 4-diaruinoQ-methyl-S-methoxy-l:1-azobeuzene Bright red-brown. l1. Ciba red G (Schultz No. 906).. Benzene-azo-a naphthylamine Deep brown. 12. Ciba blue 2B (Schultz N o. 181) Benzene-azo-wnaphthylamine Deep brown. 13. Ciha grey G (Schultz No. 899) Benzene-azo-a naphtl1ylamine Brown. 14. Cibanone yellow R (Schultz No. 79 Bcnzeue-azo-a-naphthylamine Dark brown. 15. Cibanone orange R (Schultz No. 792) Benzene-azo-a-naphthylarnine Dark brown. 16. Cibanone blue G (Colour Index No. 1115) 4-chloro-4-aruino-2-methyl-5me Dark olive. 17. Cibanone green 13 (Schultz No. 793) l3enzene-azo-anaphtl1ylamiue i Dark brown. 18. Clbanonc green B (Schultz No. 793) 4: 4-(liamino-Z-methyl-S-mcthox zene Dark green. 19. The Sodium salt of the sulfuric acid ester of leuco-indigo 4-chloro-4-amino 2-rncthy1-5-mothoxy-1;1-azobenzen Brownish-ollve.

Ewample 3 What I claim is 1. Process .for roducin fast tints on the A Vat is prepared in the followln g manp fiber, consisting in coupling reduced Vat-dyestuffs, with whichthe fiber has been impregnated with diazo-compounds. y

2. Process for producing fast tints on the fiber, consisting in coupling reduced vat-dyestutfs, with-which the fiber has been impregnated with diazotized amino-azo-dyestuffs. r i

In witness whereof I have hereunto signed my name this 19th day of August, 1929.

ROBERT HALLER. 

